JP7195668B2 - Production and use of N^N^C^O-type tetradentate platinum(II) complex - Google Patents

Description

The present invention relates to a new type of N̂N̂ĈO tetradentate platinum(II) complex metal-organic materials, and more particularly to phosphorescent dopant materials with photon emission in the light-emitting layer of OLED light-emitting devices.

Organic Light-Emitting Diodes (OLEDs) have advantages such as self-luminescence, wide viewing angle, infinitely high contrast, low power consumption, very high reaction speed and potential flexibility and folding performance. , has been much more widely considered.

In the field of OLED materials, the development of dopant materials for phosphorescent OLED light-emitting layers is rapid and mature, which are mainly based on heavy metal organic complexes such as iridium, platinum, europium, osmium. Phosphorescent materials can fully utilize the energy of singlet and triplet excitons in the luminescence process, and in theory, their quantum efficiency can reach 100%. is.

Recently, phosphorescent OLED materials based on platinum(II) have shown excellent display performance. Platinum(II) is generally a tetra-coordinated site, and tetradentate complexes can be engineered to form metal-organoplatinum(II) complexes with unique configurations. However, the development of platinum (II) complexes has lagged behind the application of mature iridium (III) complex luminescent materials. ) is important for promoting commercial applications of the complexes.

The novel N̂N̂ĈO tetradentate platinum(II) complex metal organic material according to the present invention has the structure shown in the formula below.

wherein R ₁ to R ₁₅ are independently hydrogen, deuterium, sulfur, halogen, hydroxyl group, acyl group, alkoxy group, acyloxy group, amino group, nitro group, acylamino group, cyano group, carboxyl group, styrenyl group, aminocarbonyl group, carbamoyl group, benzylcarbonyl group, aryloxy group, diarylamine group, saturated alkyl group containing 1-30 C atoms, unsaturated alkyl group containing 1-20 C atoms, 5-30 substituted or unsubstituted aryl groups containing from 5 to 30 C atoms, substituted or unsubstituted heteroaryl groups containing from 5 to 30 C atoms, or adjacent R ₁ to R ₁₅ are covalently bonded to each other combine to form a ring.

Preferably, R ₁ to R ₁₅ are independently hydrogen, halogen, amino group, nitro group, cyano group, diarylamine group, saturated alkyl group containing 1 to 10 C atoms, halogen or one or more C ₁ aryl group containing 5 to 20 C atoms, substituted or unsubstituted by -C ₄ alkyl group, halogen or substituted or unsubstituted by one or more C ₁ -C ₄ alkyl groups selected from heteroaryl groups containing 5 to 20 C atoms, or adjacent R ₁ to R ₁₅ are covalently linked to each other to form a ring, and said halogen is F, Cl, Br; .

Preferably, of the 15 groups R ₁ to R ₁₅ , 0 to 3 groups are independently substituted or substituted with diarylamine groups, halogens or 1 to 3 C ₁ -C ₄ alkyl groups. an aryl group containing 5 to 10 C atoms unsubstituted, an N-containing heteroaryl group containing 5 to 10 C atoms substituted or unsubstituted by halogen or 1 to 3 C1-C4 alkyl groups and the other groups independently represent hydrogen or saturated alkyl groups containing 1-8 C atoms, said halogen being F, Cl.

Preferably, of the 15 groups R ₁ to R ₁₅ , 0 to 3 groups independently represent a diphenylamino group, phenyl group, pyridyl group, carbazolyl group, and the other groups independently represent hydrogen, Fluorine represents a saturated alkyl group containing 1 to 4 C atoms.

wherein R ₁ to R ₅ are independently substituted by hydrogen, halogen, diarylamine group, saturated alkyl group containing 1 to 10 C atoms, halogen or one or more C ₁ to C ₄ alkyl groups , or an aryl group containing 5 to 20 C atoms unsubstituted, containing 5 to 20 C atoms substituted or unsubstituted by halogen or one or more C ₁ -C ₄ alkyl groups selected from heteroaryl groups or adjacent R ₁ to R ₅ are covalently linked to each other to form a ring, said halogen being F, Cl, Br;

Preferably, in the five groups R ₁ -R ₅ , 0-3 groups are independently substituted or substituted with diarylamine groups, halogens or 1-3 C ₁ -C ₄ alkyl groups. an aryl group containing 5 to 10 C atoms unsubstituted, a heteroaryl group containing 5 to 10 C atoms substituted or unsubstituted by halogen or 1 to 3 C ₁ -C ₄ alkyl groups and the other groups independently represent hydrogen, halogen or saturated alkyl groups containing 1-8 C atoms, said halogen being F, Cl.

Preferably, of the five groups R ₁ to R ₅ , 0 to 3 groups are independently diphenylamino groups, phenyl groups substituted or unsubstituted with C ₁ to C ₄ alkyl groups, Pyridyl group, carbazolyl group, other groups independently represent hydrogen, fluorine, saturated alkyl groups containing 1 to 4 C atoms.

For the purposes of this application, unless otherwise specified, the terms halogen, alkyl, alkenyl, aryl, acyl, alkoxy, heteroaromatic or heteroaryl have the following meanings: can have

Said halogen or halo includes fluorine, chlorine, bromine, iodine, preferably F, Cl, Br, particularly preferably F or Cl, most preferably F.

The aryl group and heteroaryl group that are linked by the covalent bond to form a ring have 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and Aryl groups consisting of one aromatic ring or multiple condensed aromatic rings are preferred. Suitable aryl groups are, for example, phenyl, naphthyl, acenaphthenyl, dihydroacenaphthenyl, anthryl, fluorenyl, phenalenyl. The aryl group is unsubstituted (all substitutable carbon atoms have a hydrogen atom) or substituted at one or more or all substitutable positions of the aryl group. Suitable substituents are as follows. For example halogen, preferably F, Br or Cl. It is an alkyl group, preferably an alkyl group having 1 to 20, 1 to 10 or 1 to 8 carbon atoms, with methyl, ethyl and carbonyl being particularly preferred. It is an aryl group, preferably a _{subsubstituted} or unsubstituted C5, _C6 aryl group or fluorenyl group. It is a heteroaryl group, preferably a heteroaryl group containing at least one nitrogen atom, with a pyridyl group being particularly preferred. It is particularly preferred that aryl groups have substituents selected from F and t-butyl groups, any aryl group being a given aryl group or a C ₅ , C ₆ aryl group substituted by at least one of said substituents. is preferred, and C5, C6 aryl groups are particularly preferred to have 0, ₁ or ₂ of said substituents, and _C5 , _C6 aryl groups are unsubstituted phenyl groups or substituted phenyl groups. It is particularly preferred to have, for example, a biphenyl group, a phenyl group meta-substituted by two t-butyl groups.

An unsaturated alkyl group containing 1 to 20 C atoms is preferably an alkenyl group, more preferably an alkenyl group having one double bond, especially an alkenyl group having a double bond and 1 to 8 carbon atoms. preferable.
Said alkyl groups include alkyl groups having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, desirably 1 to 4 carbon atoms. The alkyl group may be branched or straight chain, cyclic, and may be interrupted by one or more heteroatoms, preferably N, O, or S. The alkyl group can also be substituted with one or more halogen or substituents of the aryl groups described above. Similarly, for alkyl groups, it is possible to have one or more aryl groups, all of the aryl groups mentioned above being applicable for this purpose, alkyl groups being particularly methyl, ethyl, isopropyl, Those selected from n-propyl, isobutyl, n-butyl, tert-butyl, sec-butyl, isopentyl, cyclopropyl and cyclohexyl groups are preferred.

The acyl groups described above are those attached to the CO group by a single bond, such as the alkyl groups used herein.

The acyl groups described above are those directly attached to oxygen with a single bond, such as the alkyl groups used herein.

said heteroaryl group is associated with an aromatic, cyclic group and has 1 oxygen or sulfur atom or from 1 to 4 nitrogen atoms, or a combination of 1 oxygen or sulfur atom and up to 2 nitrogen atoms; and further include substituted and benzopyridine and fused derivatives thereof, e.g., connected via one ring-forming carbon atom thereof, wherein said heteroaryl group comprises one or more aryl groups The mentioned substituents can be substituted.

In some embodiments, heteroaryl groups can be independent 5-, 6-membered aromatic heterocycles containing 0, 1, or 2 substituents as described above. Typical examples of heteroaryl groups include unsubstituted furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, indole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, imidazoles, benzimidazoles, pyrazoles, indazoles, tetrazoles, quinolines, isoquinolines, pyridazines, pyrimidines, purines and pyrazines, furans, 1,2,3-diazoles, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, triazoles , benzotriazole, pteridine, benzoxazole, diazole, benzopyrazole, quinolidine, cinnoline, phthalazine, quinazoline and quinoxaline and mono- or di-substituted derivatives thereof. In some embodiments, the substituents are halo, hydroxy, cyano, O—C _1-6 alkyl, C _1-6 alkyl, hydroxyC _1-6 alkyl and amino-C _1-6 alkyl. be.
Specific examples shown below include, but are not limited to, the following structures.

The structural formula of the ligand, which is the precursor of the above complex, is as follows.

wherein R ₁ to R ₁₅ are independently hydrogen, halogen, amino group, nitro group, cyano group, diarylamine group, saturated alkyl group containing 1 to 10 C atoms, halogen or one or more C ₁ an aryl group containing 5 to 20 C atoms substituted or unsubstituted by a -C ₄ alkyl group, a halogen containing 5 to 20 C atoms or one or more C ₁ -C ₄ alkyl groups R 1 to R 15 are selected from substituted or unsubstituted heteroaryl groups, or adjacent R ₁ to R ₁₅ are covalently linked to each other to form a ring.

である。 Preferably,

is.

wherein R ₁ '-R ₅ ' are independently substituted with hydrogen, halogen, diarylamine group, saturated alkyl group containing 1-10 C atoms, halogen or one or more C ₁ -C ₄ alkyl groups an aryl group containing 5 to 20 C atoms substituted or unsubstituted, 5 to 20 C atoms substituted or unsubstituted by halogen or one or more C ₁ -C ₄ alkyl groups or adjacent R ₁ ' to R ₅ ' are covalently linked to each other to form a ring, and said halogen is F, Cl or Br.

Use of said complexes in OLED light-emitting devices.

Platinum (II) complexes having the above structure can be used to fabricate OLED devices by thermal deposition and solution processing.

An organic light-emitting device comprising one or more of the above complexes.

Here, the complex is applied in the form of a layer in the device by thermal evaporation.

Here, the complex is applied in the form of a layer in the device by spin coating.

Here, the complex is applied in the form of a layer on the device by inkjet printing.

The organic light-emitting device emits reddish-orange light when an electric current is applied.

From the organometallic complexes in the present invention, red-orange light OLED devices with high fluorescence quantum efficiency, good thermal stability and low quenching constant, high luminous efficiency and low roll-off can be produced.

It is a schematic diagram of the structure of the organic electroluminescent element of this invention.

The invention will now be described in more detail with reference to examples.

In the method for producing the complex, as shown below, a substrate S3 is obtained from initial substrates S1 and S2 by Buchwald-Hartwig coupling reaction, a substrate S5 is obtained from S3 and S4 by Buchwald-Hartwig coupling reaction, and S5 by the action of pyridine hydrochloride to give S6 and reacting S6 with K ₂ PtCl ₄ to give the desired product P.

The initial substrates and solvents for compound synthesis in the present invention are purchased from manufacturers known to those skilled in the art, such as Antaiji, Baileiwei, and Aladdin.

Example 1:

Synthesis of compound 3: 19.92 g (0.10 mol) of compound 1, 26.92 g (0.10 mol) of compound 2, 450 mg (0.02 eq., 2 mmol) of palladium acetate 23, 1.05 g (0.04 eq.) ., 4 mmol) of triphenylphosphine, 22.44 g (2.0 eq., 0.20 mol) of potassium t-butoxy are added to the flask, 200 mL of dioxane is added, and the reaction is heated to reflux for 8 hours under nitrogen protection. . After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 32.18 g of the desired product compound 3 were obtained. The yield is 90% and the purity is 99.5%.

Synthesis of compound 5: 17.88 g (50 mmol) of compound 3, 11.75 g (50 mmol) of compound 4, 225 mg (0.02 eq., 1 mmol) of palladium acetate, 0.53 g (0.04 eq., 2 mmol) of Triphenylphosphine, 11.22 g (2.0 eq., 0.10 mol) of potassium t-butoxy are added to the flask, 200 mL of dioxane is added, and the reaction is heated to reflux for 8 hours under nitrogen protection. After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 23.83 g of the desired product compound 5 were obtained. The yield is 88% and the purity is 99.9%.

Synthesis of compound 6: Take 5.42 g (10 mmol) of compound 5 and 30 g of pyridine hydrochloride, heat to 200° under nitrogen protection and react for 8 hours. After stopping the reaction, extraction was performed with appropriate amounts of water and ethyl acetate, and the organic phase was collected, dried, and after removing the solvent with rotavap, was recrystallized with methanol to obtain 4.48 g of the desired product compound 6. The yield is 85% and the purity is 99.9%. Mass spectrum (ESI ^- ) ([MH] ^- ) C ₃₆ H ₃₇ N ₃ O calc: 526.29; found: 526.26.

Synthesis of compound P1: 1.06 g (2.0 mmol) of compound 6, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg (1.2 eq., 2.4 mmol) of tetrachloroplatinic acid. Potassium is dissolved in 25 mL of acetic acid, and after evacuating and replacing with nitrogen several times, the mixture is stirred and heated to 130° C. and reacted for 12 hours. After the reaction was completed, the solvent was removed by cooling with a rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then the solvent was removed with a rotavap. The resulting crude product was sublimed in vacuo by xane/ethyl acetate based column chromatography to give 648 mg of a red solid. The yield is 45% and the purity is 99.9%. Mass spectrum (ESI ⁻ ) ([M−H] ⁻ ) C ₃₆ H ₃₄ N ₃ OPt theoretical: 719.24; found: 719.23.

Example 2:

Synthesis of compound 8: 27.53 g (0.10 mol) of compound 7, 26.92 g (0.10 mol) of compound 2, 450 mg (0.02 eq., 2 mmol) of palladium acetate, 1.05 g (0.04 eq. , 4 mmol) of triphenylphosphine, 22.44 g (2.0 eq., 0.20 mol) of potassium t-butoxy are added to the flask, 250 mL of dioxane is added, and the reaction is heated under reflux for 8 hours under nitrogen protection. After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 40.82 g of the desired product compound 8 were obtained. The yield is 88% and the purity is 99.5%.

Synthesis of compound 10: 23.18 g (50 mmol) of compound 8, 14.56 g (50 mmol) of compound 9, 225 mg (0.02 eq., 1 mmol) of palladium acetate, 0.53 g (0.04 eq., 2 mmol) of Triphenylphosphine, 11.22 g (2.0 eq., 0.10 mol) of potassium t-butoxy are added to the flask, 200 mL of dioxane is added, and the reaction is heated to reflux for 8 hours under nitrogen protection. After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 30.32 g of the desired product compound 10 were obtained. The yield is 90% and the purity is 99.9%.

Synthesis of compound 11: Take 6.74 g (10 mmol) of compound 10 and 40 g of pyridine hydrochloride, heat to 200° C. under nitrogen protection and react for 8 hours. After stopping the reaction, extraction was performed with appropriate amounts of water and ethyl acetate, and the organic phase was collected, dried, and after removing the solvent with rotavap, was recrystallized with methanol to obtain 5.28 g of the desired product compound 11. The yield is 80% and the purity is 99.9%. Mass spectrum (ESI ⁻ ) ([M−H] ⁻ ) C ₄₆ H ₄₈ N ₃ O calc: 658.39; found: 658.37.

Synthesis of compound P6: 1.32 g (2.0 mmol) of compound 11, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg (1.2 eq., 2.4 mmol) of tetrachloroplatinic acid. Potassium is dissolved in 25 mL of acetic acid, and after evacuating and replacing with nitrogen several times, the mixture is stirred and heated to 130° C. and reacted for 12 hours. After the reaction was completed, the solvent was removed by cooling with a rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then the solvent was removed with a rotavap. The resulting crude product was sublimed in vacuo by xane/ethyl acetate based column chromatography to give 716 mg of a red solid. The yield is 42% and the purity is 99.9%. Mass spectrum (ESI ⁻ ) ([M−H] ⁻ ) C ₄₆ H ₄₆ N ₃ OPt theoretical: 851.34; found: 851.32.

Example 3:

Synthesis of compound 13: 19.92 g (0.10 mol) of compound 1, 24.12 g (0.10 mol) of compound 12, 450 mg (0.02 eq., 2 mmol) of palladium acetate 23, 1.05 g (0.04 eq.) ., 4 mmol) of triphenylphosphine, 22.44 g (2.0 eq., 0.20 mol) of potassium t-butoxy are added to the flask, 250 mL of dioxane is added, and the reaction is heated to reflux for 8 hours under nitrogen protection. . After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 32.36 g of the desired product compound 13 were obtained. The yield is 90% and the purity is 99.5%.

Synthesis of compound 15: 17.98 g (50 mmol) of compound 13, 19.78 g (50 mmol) of compound 14, 225 mg (0.02 eq., 1 mmol) of palladium acetate, 0.53 g (0.04 eq., 2 mmol) of Add triphenylphosphine, 11.22 g (2.0 eq., 0.10 mol) of potassium t-butoxy to the flask, add 250 mL of dioxane, and heat to reflux for 8 hours under nitrogen protection. After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 28.64 g of the desired product compound 15 were obtained. The yield is 85% and the purity is 99.9%.

Synthesis of compound 16: 6.74 g (10 mmol) of compound 15 and 40 g of pyridine hydrochloride are taken, heated to 200° under nitrogen protection and reacted for 8 hours. After stopping the reaction, extraction was performed with appropriate amounts of water and ethyl acetate, and the organic phase was collected, dried, and after removing the solvent with rotavap, was recrystallized with methanol to obtain 5.61 g of the desired product compound 16. The yield is 85% and the purity is 99.9%. Mass spectrum (ESI ⁻ ) ([M−H] ⁻ ) C ₄₆ H ₄₈ N ₃ O calc: 658.39; found: 658.37.

Synthesis of compound P24: 1.32 g (2.0 mmol) of compound 16, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg (1.2 eq., 2.4 mmol) of tetrachloroplatinic acid. Potassium is dissolved in 25 mL of acetic acid, and after evacuating and replacing with nitrogen several times, the mixture is stirred and heated to 130° C. and reacted for 12 hours. After the reaction was completed, the solvent was removed by cooling with a rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then the solvent was removed with a rotavap. The resulting crude product was sublimed in vacuo by xane/ethyl acetate based column chromatography to give 682 mg of a red solid. The yield is 40% and the purity is 99.9%. Mass spectrum (ESI ⁻ ) ([M−H] ⁻ ) C ₄₆ H ₄₆ N ₃ OPt theoretical: 851.34; found: 851.32.

Example 4:

Synthesis of compound 18: 30.34 g (0.10 mol) of compound 17, 26.92 g (0.10 mol) of compound 2, 450 mg (0.02 eq., 2 mmol) of palladium acetate 23, 1.05 g (0.04 eq.) ., 4 mmol) of triphenylphosphine, 22.44 g (2.0 eq., 0.20 mol) of potassium t-butoxy are added to the flask, 300 mL of dioxane is added, and the reflux reaction is heated for 8 hours under nitrogen protection. . After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. yielded 44.25 g of the desired product compound 18. The yield is 90% and the purity is 99.5%.

Synthesis of compound 20: 25.58 g (50 mmol) of compound 18, 16.96 g (50 mmol) of compound 19, 225 mg (0.02 eq., 1 mmol) of palladium acetate, 0.53 g (0.04 eq., 2 mmol) of Add triphenylphosphine, 11.22 g (2.0 eq., 0.10 mol) of t-butoxypotassium to the flask, add 300 mL of dioxane, and conduct a reflux reaction with heating for 8 hours under nitrogen protection. After the reaction was stopped, it was cooled to room temperature and the solvent was removed by rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. 30.75 g of the desired product compound 20 were obtained. The yield is 82% and the purity is 99.9%.

Synthesis of compound 21: Take 7.50 g (10 mmol) of compound 20 and 50 g of pyridine hydrochloride, heat to 200° under nitrogen protection and react for 8 hours. After stopping the reaction, extraction was performed with appropriate amounts of water and ethyl acetate, and the organic phase was collected, dried, and after removing the solvent with rotavap, was recrystallized with methanol to obtain 5.89 g of the desired product compound 21. The yield is 80% and the purity is 99.9%. Mass spectrum (ESI ^- ) ([MH] ^- ) C ₅₂ H ₅₂ N ₃ O calc: 734.42; found: 734.40.

Synthesis of compound P45: 1.47 g (2.0 mmol) of compound 21, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg (1.2 eq., 2.4 mmol) of tetrachloroplatinic acid. Potassium is dissolved in 25 mL of acetic acid, and after evacuating and replacing with nitrogen several times, the mixture is stirred and heated to 130° C. and reacted for 12 hours. After the reaction was completed, the solvent was removed by cooling with a rotavap, followed by extraction with an appropriate amount of water and ethyl acetate. The organic phase was collected, dried over anhydrous magnesium sulfate, and then the solvent was removed with a rotavap. The resulting crude product was sublimed in vacuo by xane/ethyl acetate based column chromatography to give 780 mg of a red solid. The yield is 42% and the purity is 99.9%. Mass spectrum (ESI ^- ) ([MH] ^- ) C ₅₀ H ₅₀ N ₃ OPt calc: 927.37; found: 927.35.

For the Pt(II) complexes of the examples, orange-red luminescence remarkably appears in the dichloromethane solution. As shown in the table below.

Application examples of the compounds of the present invention are shown below.
ITO/TAPC (60 nm)/TCTA:Pt(II) (40 nm)/TmPyPb (30 nm)/LiF (1 nm)/Al (80 nm)

Element manufacturing method:

A transparent anodized indium tin (ITO, 20) (10Ω/sq) glass substrate 10 is ultrasonically cleaned using acetone, ethanol, and distilled water in sequence and treated with oxygen plasma for 5 minutes.

Next, the ITO substrate is attached to the substrate holder of the vacuum vapor deposition apparatus. In the vapor deposition apparatus, the system pressure was set to 10 ^-6 torr. to control.

Subsequently, a 60 nm hole transport layer (30) material TAPC is deposited on the ITO substrate.

After that, a 40 nm-thick light-emitting layer material (40) TCTA is deposited, in which platinum (II) complex dopant agents with different mass fractions are doped.

A 30 nm thick electron transport layer (50) material TmPyPb is then deposited.

After that, LiF with a thickness of 1 nm is vapor-deposited to form an electron injection layer (60).

Finally, Al with a thickness of 80 nm is deposited as a cathode (70) to complete the device package. Shown in FIG.

The structure and manufacturing method of the device are exactly the same, the difference being that the organometallic complexes P0, P1, P6, P24 and P45 are sequentially used as the dopant agent and dopant concentration in the light emitting layer. Here, Pt0 is a conventional O^N^N^O red light material.

The comparison results of the devices are shown in the table below.

The above ITO/HTL-1 (60 nm)/EML-1:Pt(II) (40 nm)/ETL-1 (30 nm )/LiF (1 nm)/Al (80 nm) device. Referring to the performance of the devices with Pt0, the devices with tetradentate platinum(II) complexes P1, P6, P24, P45 all have different degrees of reduction in the starting voltage V _on compared to the devices with Pt0. At the same time, under the condition of 1000 cd/A, the devices based on P1, P6, P24 and P45 have different current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) than P0. There is a degree of improvement, especially for P45, which is clearly improved in terms of current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE). The efficiencies of P1, P6, P24 and P45 all improve to different degrees when the dopant concentration of the tetradentate platinum(II) complex is increased. P45 has a larger positional resistance group than P1, P6, and P24, reduces intermolecular aggregation, avoids exciplex formation, and increases luminous efficiency.

In the tetradentate platinum (II) complex according to the present invention, the central platinum is in the form of a 6-membered ring + 6-membered ring + 5-membered ring chelate coordination, the formed complex is stable and has an excellent rigid structure, Dissipation of non-radiative energy such as intramolecular rotation and vibration can be greatly reduced, which is advantageous for improving the luminous efficiency and performance of the platinum (II) complex. At the same time, the triphenylamine structural part in the ligand skeleton can be easily added with different substituents, which is easy to achieve optimization and control of the molecular structure.

As described above, the performance of the organic electroluminescent device produced by the present invention shows a good improvement in performance compared to the reference device, and the metal-organic The material has great application value.

Claims (14)

N^N^C^O tetradentate platinum(II) complex having the structure shown in the formula,

In the formula, R ₁ to R ₁₅ are independently hydrogen, deuterium , halogen , hydroxyl group, acyl group, alkoxy group, acyloxy group, amino group, nitro group, acylamino group, cyano group, carboxyl group, styrenyl group, amino carbonyl group, carbamoyl group, benzylcarbonyl group, aryloxy group, diarylamine group, saturated alkyl group containing 1 to 30 C atoms, unsaturated alkyl group containing 2 to 20 C atoms, 5 to 30 is selected from a substituted or unsubstituted aryl group containing C atoms, a substituted or unsubstituted heteroaryl group containing 5 to 30 C atoms, or adjacent R ₁ to R ₁₅ are covalently bonded to each other; N̂N̂ĈO tetradentate platinum(II) complexes forming rings. R ₁ to R ₁₅ are independently hydrogen, halogen, amino group, nitro group, cyano group, diarylamine group, saturated alkyl group containing 1 to 10 C atoms, halogen or one or more C ₁ to C ₄ an aryl group containing 5 to 20 C atoms substituted or unsubstituted by an alkyl group, halogen or 5 to 20 substituted or unsubstituted by one or more C ₁ -C ₄ alkyl groups heteroaryl groups containing 1 C atom, or adjacent R ₁ to R ₁₅ are covalently linked to each other to form a ring, and said halogen is F, Cl, Br. Described complex. Of the 15 groups R ₁ to R ₁₅ , 0 to 3 groups are independently substituted or unsubstituted with diarylamine groups, halogens or 1 to 3 C ₁ -C ₄ alkyl groups. an aryl group containing 5-10 C atoms, an N-containing heteroaryl group containing 5-10 C atoms substituted or unsubstituted with halogen or 1-3 C ₁ -C ₄ alkyl groups; and the other groups independently represent hydrogen or saturated alkyl groups containing 1 to 8 C atoms, and said halogens are F, Cl. Of the 15 groups represented by R ₁ to R ₁₅ , 0 to 3 groups independently represent a diphenylamino group, phenyl group, pyridyl group or carbazolyl group, and the other groups independently represent hydrogen, fluorine, 1 4. A complex according to claim 3, representing a saturated alkyl group containing ˜4 C atoms. having the structure shown in the formula below,

wherein R ₁ '-R ₅ ' are independently substituted with hydrogen, halogen, diarylamine group, saturated alkyl group containing 1-10 C atoms, halogen or one or more C ₁ -C ₄ alkyl groups an aryl group containing 5 to 20 C atoms substituted or unsubstituted, 5 to 20 C atoms substituted or unsubstituted by halogen or one or more C ₁ -C ₄ alkyl groups or adjacent R ₁ ' to R ₅ ' are covalently bonded to each other to form a ring, and the halogen is F, Cl or Br. Complex. Of the five groups R ₁ '-R ₅ ', 0-3 groups are independently substituted or substituted with diarylamine groups, halogens or 1-3 C ₁ -C ₄ alkyl groups. an aryl group containing 5 to 10 C atoms unsubstituted, a heteroaryl group containing 5 to 10 C atoms substituted or unsubstituted by halogen or 1 to 3 C ₁ -C ₄ alkyl groups and the other groups independently represent hydrogen, halogen or saturated alkyl groups containing 1 to 8 C atoms, said halogens being F, Cl. Of the five groups R ₁ ' to R ₅ ', 0 to 3 groups are independently diphenylamino, C ₁ -C ₄ alkyl substituted or unsubstituted phenyl, pyridyl A complex according to claim 6, wherein the group represents a carbazolyl group and the other groups independently represent hydrogen, fluorine, saturated alkyl groups containing 1 to 4 C atoms. The complex according to claim 1, having the structure:

9. A complex according to claim 8, having the structure:

A precursor of the complex according to any one of claims 1 to 9, which is a ligand and whose structural formula is shown below:

wherein R ₁ to R ₁₅ are independently hydrogen, halogen, amino group, nitro group, cyano group, diarylamine group, saturated alkyl group containing 1 to 10 C atoms, halogen or one or more C ₁ aryl group containing 5 to 20 C atoms, substituted or unsubstituted by -C ₄ alkyl group, halogen or substituted or unsubstituted by one or more C ₁ -C ₄ alkyl groups Precursors selected from heteroaryl groups containing 5 to 20 C atoms, or adjacent R ₁ to R ₁₅ are covalently linked to each other to form a ring. The structural formula is shown below,

wherein R ₁ '-R ₅ ' are independently substituted with hydrogen, halogen, diarylamine group, saturated alkyl group containing 1-10 C atoms, halogen or one or more C ₁ -C ₄ alkyl groups an aryl group containing 5 to 20 C atoms substituted or unsubstituted, 5 to 20 C atoms substituted or unsubstituted by halogen or one or more C ₁ -C ₄ alkyl groups or adjacent R ₁ ' to R ₅ ' are covalently bonded to each other to form a ring, and the halogen is F, Cl or Br. precursor. A method for synthesizing the tetradentate platinum (II) complex according to any one of claims 1 to 9,
Substrate S3 was obtained from initial substrates S1 and S2 by Buchwald-Hartwig coupling reaction, substrate S5 was obtained from S3 and S4 by Buchwald-Hartwig coupling reaction, and S5 was demethylated by the action of pyridine hydrochloride to obtain S6. and reacting S6 with K ₂ PtCl ₄ to obtain the target product P, the reaction formula being as follows.

Use of a complex according to any one of claims 1 to 9 in an OLED light-emitting device. The use according to claim 13, wherein the complex according to any one of claims 1 to 9 is a phosphorescent-doped material having photon-emitting action in the light-emitting layer.

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